Stable vitamin containing products



Patented June 4, 1946 2,401,293 STABLE VITAMIN CONTAINING PRODUCTS Loran 0. Buxton, Newark, and Harry J. Konen, East Orange, N. 1., assignors to National Oil Products Company, Harrison, N. 1., a corporation of New Jersey No Drawing. Application May 7, 1942, Serial No. 442,079

8 Claims. (Cl. 99-11) This invention relates to stable vitamin-containing food products and more particularly to dry food products containing fat-soluble vitamins in a stable form.

Much work has been done in the prior art in the preparation of fat-soluble vitamin-containing food products in a dry form. One of the problems involved has been to produce such products which are substantially unchanged in taste and odor by having vitamin materials added thereto. However, by far the greatest problem involved has been to devise means of inhibiting the oxidative destruction of the vitamins after the have been incorporated into the dry carrier.

It is rather common practice for feed manufacturers and farmers to incorporate fat-soluble vitamin-containing materials, e. g., cod liver oil, sardine oil, etc., into poultry and animal feeds in order to fortify such feeds with vitamins A and D. However, the vitamins which are contained in such stock feeds are readily susceptible to oxidative deterioration and destruction; consequently, it is necessary in order to provide feeds with the proper vitamin potency to admix the vitamin-containing material therewith only shortly before feeding the stock food. Various proposals have been made for the production of stable vitamin-containing materials of high potency in a dry, granular form which may be admixed with stock and poultry feeds in order to provide vitamin-fortified feeds which are stable over a relatively long period of time. However, as yet, no stable satisfactoryproducts have been made available.

One proposal has been made to add small amounts of vitamin-containing materials to vegetable meals containing at least 5 per cent of fatty material; however, such a proposal has not proved to be entirel satisfactory. Another suggestion has been to impregnate dried yeast with cod liver oil and then to coat the impregnated particles with Karaya gum by dispersin the yeast particles in a solution of the gum and subsequently drying the coated particles. Another proposal has been to mix fish liver oils with liquid paraffin wax and then to impregnate dry, granular vegetable material therewith, and cooling the mass to give Vegetable particles coated and/or impregnated with a vitamin-containing oil enclosed in a film of paraflin wax. A further proposal has been to combine a wax and a gum in a similar process. The use of waxes, gums, etc., to protect vitamins against oxidizing influences of the'atmosphere is not very satisfactory, since not only have the products not proved to be very stable as regards the destruction of the vitamins, but also the use of waxes and sums is highly undesirable from a physiological standpoint, since such materials are not readily assimilable by the body. Also, such substances tend to interfere with the proper absorption by the body of the vitamins contained in the food or feed.

It is the object of this invention to provide improved fat-soluble vitamin-containing food products in substantially dry form.

A further object of the invention is to provide fat-soluble vitamin-containing food products in dry form having enhanced stability.

Another object of the invention is to provide improved products for fortification of foods for human and animal consumption comprising a vitamin A and/ or D containing material dispersed in a dry carrier, the vitamins contained therein being highly stable towards deteriorative oxidation.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

We have found that highly stable fat-soluble vitamin-containing food products may be readily prepared by intimately mixing fat-soluble vitamin-containing material with comminuted or otherwise finely divided vegetable material capable of absorbing large amounts of fatty material and preferably a vegetable material containing relatively large amounts of natural antioxidants. The mixture thus obtained is then intimately mixed with a relatively large amount of crude vegetable oil; however. in all cases keeping the oil content of the product below a, point where the product would tend to lose its dry characteristics and become oily. The products which are produced by this process are dry. granular or otherwise finely divided and may be readil admixed, with poultry and stock feeds or with various food products for human consumption, such as cereals, flour, etc., or used for other suitable purposes. The vitamin content of these products is very stable and little or no destruction thereof will result even on storing these products under atmospheric conditions for relatively long periods of time. Alternatively, the vitamin-containing products may be prepared by a one-step process; that is, the vitamin-containing material maybe dissolved in the crude vegetable oil and the mixture of the crude vegetable oil and the vitamin-containing material admixed with the.

dry, finely divided vegetable material all at one time.

When the process is carried out by either of the two embodiments set forth above. the crude vege- 3 table oil as it is absorbed into the cellular structure of the finely divided vegetabl material carries with it the tat-soluble vitamin-containing material. The fat-soluble vitamins are thus comthe atmosphere. Furthermoreiby thus beingcar ried into the innermost cellular structure of the vegetable material, the fat-soluble vitamins are brought into intimate contactnwith the natiiral antioxidants of the vegetablernatriali 'lhese antioxidants as well as the.:.:natu"ral;,antioxidants contained in the crude vegetable oilru rther pr tect the fat-soluble vitamins frdr'r'i "detiaribration by oxidizing influences. The conjoint action of these three factors, i. e., the physical eigclusipm from the atmosphere and its oxidizing influences, the protection afl'orded by the natural, antio xie dants of the finely ylded vegetable material} and plfotection Providedrby e natural antioxidantsrconta'ined in the crude 5 vegetable oil; is. :g 20

eifectiv'e in I protecting the i'at-solubl'e vitamins from oxidativedeterioration and "destruction that no'loss'inlvitamin Dlpotency and little or no loss of vitamin A potencyi-in-the finalproduct wil1 resuit over periods or six months and longer even 26 though the carrier .is stored under conditions which 'are con'ducive to oxidation and destruction oi the-vitamin contentthereoi'. Feed-manufac= turers have been trying', 10 ears; t t i results; made "available by this inv'ention. so

By merely mixing an ordinary'vitamin-con taining oil, e. g1, cod liver'oil; sardine oil, etc; with an 'ordinarysto'ck or poultry-deed; no such 'resultsfvvill beobtaihed. i somehbs'oi'ptionoftiie vitamin-'containingf oil into the reed "will take 36 blaceibut a lar e proportion" ofitvfvill remain on thoute'r surface er -the r ed sarticiesgandi be readily s'i'iscehtlble to oiiidati6n -anddestructioni Furthermore, such oxidation will induce oxidation ar -any vitamimcentaining ateriai that may 40 havebee'n absorb t 'tne c'eu structure oritrie feed materiah- Co 's'quently; th *result 'is 'that sueu reeu io e thiijvitamihf potency yew-rapid i .i {tn-erupt? few-days. 45

amount qr iatty' r'fiaterlal; suitable yegetable m; to

corn oil'me'alg'dried di'stillers grain vegetableinaterialsemployedinprodiicing ftii teams. suhtreatmeiit r appears to increasqitli materialis ic-1 mm i preferred that the soluble (dried 'distillers"corn' and/or rye sol *th'" :5 either alone or' incombination with any ofthe corporates into '1:

ently, the solvent affects the cellular structure of the vegetable material in such a manner as to make it more readily permeable by the crude vegetable oil, and once the or d anagrams is absorbed in; e H

tends to remain theref fln removal "ofthe solvent by evaporation or other suitable means, the permeability of the cell is restored to what it was .-,-befpre; butnew the; crude vegetable oil and the fat so'lubl'e vitamins" are inside the cell where they are zprotectedr irom the atmosphere. These vegetable'=niaterials; and the vegetable materials hich'd'd otreijuire such a treatment to increase their 'ai'ilnity fofiatty materials may be treated 5 with-such; solvents as mentoined hereinabove for he:,:.purpose of liberating natural antioxidants,

which, are so intimately associated with the cell structure that they do not provide as much protection for the fat-soluble vitamins as possible. The-solvent- 'tratment' aids' in making the antioxida'ntsmore readily 'available to the vita'min containing'vmaterials which are 'added and thus further aids in maintaining the stability or the final product Furthermore, if desired, these vegetable materials "may be formed into an aqueous slurry by the "addition-thereto of water and intimatelymixing. the mass. Such treatment will also tend .to liberate natural antioxidants from the vegetable materials and mak them more readily available to the vitamin-containing materials. The water'may then be removed from the "aqueous slurry: by :any suitable means, e. g,

, vacuum distillation'and the resulting dried prodmai, vegetable or fish oils rich in the fat-soluble I vitamins such 'a's cod-*liveroiL shark liver oil,

halibiitioil, sardinefoil," tuna liver' j oil-, p'almfand like oils; concentrates "thereof orsuch 'oils foi'ti-' fled with" vitamin concentratess Other sources of the iat soluble' vitamins' such as antirachitic ac tivated sterols and the like mayalso'be used sired. I Th crude vegetable oils Which are employed in the process of -the invention- 'are' preferably unnatural; nt'ioxi'dants or' i'ractiofis ofthese oils conta'i'riing 'conceiitrated therein thnatural and:

erm oflseruun'sw oean oiiscrud cottonseed bu;

crude wheat germ oil, crude peanut oil, crude palm oil. crude cocoanut oil. crude sesame seed oil, crude rice bran oil, etc. Fractions produced from such oils by processes such as vacuum distillation or the process of copending application of L. O. Buxton, Serial No. 351,909, filed August 8, 1940, and which contain the major portion of the antioxidants originally associated with the oil may also be utilized in preparing products of the invention.

In carrying out the process of the invention, any suitable fat-soluble vitamin-containing material is intimately mixed with the finely divided vegetable material or mixture of such vegetable materials to be employed as the carrier. It is preferred to employ a vegetable meal for this purpose, and the process of the invention will be described with reference to the production of the vitamin product utilizing a vegetable meal as the carrier. The vitamin-containing material is added to the vegetable meal or mixture of meals being employed and the mass intimately and thorou'ghly mixed by any suitable means, for example in a mechanical feed mixer, or the like. The amount of vitamin-containing material which is mixed with the vegetable meal will vary, depending upon the potency of the vitamin-containing material and upon the potency which is desired in the final product. However, in most instances, less than per cent of the total mass will consist of the vitamin-containing material. When the vegetable material and the vitamin-containing material have been thoroughly mixed, the crude vegetable oil is then added thereto and the mass thoroughly and intimately mixed again in order to obtain intimate contact of the crude vegetable oil with the vegetable meal and the vitamin-containing material. The crude vegetable oil is readily absorbed by the vegetable meal, and apparently in the process, as pointed out hereinabove, the vitamin-containing material is incorporated into the cells of the vegetable material and protected from the oxidizing influences of the atmosphere, both by being coated and protected from the atmosphere by means of the vegetable material and the crude vegetable oil and also by the influence of the natural antioxidants contained in the crude vegetable meal and the crude vegetable oil. Ordinarily, from about 3 per cent to about per cent of crude vegetable oil is incorporated into the product, in all cases the amount of vegetable oil incorporated being equal to or greater than the amount of vitamin-containing material incorporated. In all instances, it is preferred that a product be obtained which has a total fat content of at least 5 per cent and preferably not over per cent; however, these values will be varied, depending upon the absorptive properties of the vegetable material employed. In all instances, a stable, dry product highly suitable for use in fortifying various types of foods and feeds is obtained. Also, if desired, the product of the invention may, in some instances, be utilized as a food per se.

In certain instances, the fat-soluble vitamincontaining material may be dissolved in a minor portion (up to per cent) of the crude vegetable oil used in the process prior to admixture with the vegetable carrier. In such a case, a portion of the crude vegetable oil will be simultaneously incorporated into the solid carrier, along with the fat-soluble vitamins; and the balance of the crude vegetable oil will be incorporated into the carrier subsequent thereto.

Alternatively, as described hereinabove, the product may be prepared by dissolving the fat- 6 soluble vitamin-containing material in the crude vegetable oil, and then admixing the crude vegetable oil solution of the fat-soluble vitamins with the vegetable material to obtain the desired product. Thus, the vitamins and the crude veBetable oil are incorporated into the vegetable material in one step, thus somewhat simplifying the process; however, the results obtained by this process are not as good as when the vitamin-containing material is first admixed with the vegetable material, with the subsequent addition of the crude vegetable oil.

If it is desired to employ vegetable materials which do not have the required aiiinity for fatty materials, the vegetable material, the crude vegetable oil and the vitamin-containing material may be admixed by either of the above-described processes; and the product obtained, which will be somewhat oily, may then be contacted with an organic solvent substantially immiscible with fatty materials. As previously described, such a treatment appears to increase the ailinity of the vegetable material for fatty material; and when the solvent is removed by some suitable means, e. g., evaporation under reduced pressure, it will be found that the product which originally was of an oily nature is now non-oily, dry, and free flowing. Solvents suitable for so treating the vegetable material include methanol, ethanol, isopropanol containing at least 9 per cent of water, and similar highly polar organic solvents substantially immiscible with fatty materials. When so treating vegetable material, it is preferred to use about 1 part of solvent, by volume, to each 2 parts, by weight, of carrier, e. g., 1 ml. of solvent to 2 mos. of carrier. The solvent treatment is also quite useful in some instances for treating the products prepared from vegetable meals having a relatively high affinity for fatty materials, particularly when the larger amounts of fatty material have been incorporated into the product.

In some instances, if desired, antioxidants may be added to the dry product, employing either water-soluble or oil-soluble antioxidants. However, it is seldom necessary that this be done, since in all cases a very stable product is obtained by the process of the invention.

In order to minimize any oxidation or destruction of the vitamins during the process, it is preferred that all mixing operations be carried out under an inert atmosphere such as an atmosphere of nitrogen or carbon dioxide.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following examples which are given merely to further illustrate the invention and are not to be construed in a limiting sense, all parts given being by weight.

Example I 15 parts of a vitamin ester concentrate containing 230,000 I. U. of vitamin A and a corresponding high content of vitamin D were thoroughly mixed with 60 parts of virgin soybean oil. The soybean oil-ester concentrate mixture was then added to 319 parts of linseed oil meal and the mass fairly well mixed. 106 parts of wheat germ press cake flour were then added and the mass thoroughly and intimately mixed. At the end of four months, the vitamin A potency of the dry carrier was still the same as when it was originally prepared, i. e., slightly over 6,300 I. U. of vitamin A/gm., even though the carrier had been stored in an open container exposed to the atmosphere.

Example II A dry carrier was prepared essentially as in Example I, except that instead of using a mixture of 3 parts of linseed oil meal to 1 part of wheat germ pressed cake flour as in Example I for the finely divided vegetable material, a mixture of 2 parts of dried distillers corn solubles and 1 part each of linseed oil meal and wheat erm press cake flour were employed. Also, only 35 parts of virgin soybean oil were employed, instead of 60 parts as in Example I; A dry, free-flowing, nonoily product having a vitamin A potency of about 6,400 I. U./gm. was obtained. After being stored for five months in an open container, only slightly over 1 per cent of the vitamin A had been destroyed.

Example Ill 6 parts of an antirachitic activated sterol having a potency of 200,000 I. U. of vitamin D/gm. were dissolved in 69 parts of virgin soybean oil. The crude vegetable oil containing the vitamin dissolved therein was then mixed in a mechanical mixer with 319 parts of dried distillers corn solubles and 106 parts of linseed oil meal. The non-oily, finely divided, freeeflowing product which was obtained had a vitamin D potency of over 2200 I. U./gm. At the end of six months storage in contact with air in an oven at a temperature of 37.5" C., the potency of the vitamin product was unchanged. 1

Example IV 25 parts of a vitamin ester concentrate containing about 230,000 I. U. of vitamin A/gm. were admixed with 50 parts of virgin soybean oil, and the resulting solution thoroughly admixed with 425 parts of wheat germ pressed cake flour in a mechanical mixer. The product obtained, which was dry, non-oily, and free flowing, had a potency of 12,000 I. U. of vitamin A/gm,- and was highly suitable for the fortification of cereals, flours, and other foods for human consumption. After six months storage at room temperature in contact with the atmosphere, the product had a vitamin A potency of 11,400 I. U./gm.

Example V parts of a vitamin A alcohol concentrate containing 1,125,000 I. U. of vitamin A/gm. were dissolved in 20 parts of virgin soybean oil, and the resulting solution thoroughly admixed with 425 parts of wheat germ pressed cake flour in a mechanical mixer. The resulting product was then thoroughly admixed with 50 parts of virgin soybean oil. The product obtained, which was dry, non-oily and free flowing, had a potency of 11,800 I. U. of vitamin A/gm. After six months storage at room temperature in contact with the atmosphere, the product had a vitamin A potency of 10,700 I. U./gm.

Example VI 9 a oughly admixed in the same manner. 'Ii'l'eprod uct was slightly oily, so it was treated with methanol in order to increase the aillnity of the meal mixture for fatty material. slightly oily product were mixed with 1 part of methanol for five minutes at atmospheric pressure in a mechanical mixer to obtain initmate contact of the solvent with the meal particles. Vacuum was then applied to the mixer and the temperature of the mixer jacket raised somewhat to aid in driving off the methanol. The mass was then mixed under these conditions for about 25 minutes, at which time substantially all of the solvent had been removed. The treated product was completely non-oily and was free flowing. It had a vitamin potency of 6,520 I. U. of vitamin A/gm. and 2000 I. U. of vitamin D/gm. The product exhibited very good stability.

It is evident from the above description and examples that by the process of the invention it is possible to produce vitamin-containing products in a dry, finely divided form, which are highly stable. Such dry vitamin products are suitable for fortifying human and animal foods and feeds, such as cereals, flours, milk powders, dry or wet poultry mashes, prepared animal feeds, etc., or for the production of vitamin-containing tablets of increased stability by molding the products of the invention into tabiets'of suitable size with the aid of water, sugar solu-' tions, or by coating tablets of the productl withf an exterior sugar or like coating. etcl. In all cases, the dry vitamin product of the invention and the various food products fortilfledltherewith will have their vitamin potency remain-substantially constant over long periodsfoftimegeven when exposed to the oxidizing'influel g bffthe atmosphere. In-vie'w of the great demandffor suchia'. product, it isevfdent that the productsiofour inventil'in will be of great interest to'th' production and use of vitam terials. 1 f "f f The term crude vegetable ill; is'use'rr in the specification and claims to connotejunijefined and partially refined vegetablefoils amages thereof, i. e., vegetablefoilswhich stilfcontainj at least a major oxidant content; 2,

The in .e dm a uae at n n -7a the invention mayj 'b produced; by either'fthe' expeller, cold pr'essingj or so vent extract on methods. Such, meals f usually contain a maxi? mum of 5%1tqi: 8% fatty material andffall within the expression "{relat iYelybil-free vegetable ri qdy. t e n nt ha be deter ents c p i sk na j e l aed r ie ,a p' f 'preted' as il ustrative'a d aylpgdecrie i v on what a e' 'rl eet d t sweetness Ea l est-l a at-selu s ,;d. 9 w l some pamm n -1a fa -so ble vitamin an:

i qllsl'eiat e q .etea ge aia .nat so'pereenttrratty matei 1.

2 parts of the .t ma ria wi efleelw x q dwees:

2. A process for preparing a stable fat-soluble vitamin-containing product in a dry form which comprises admixing up to 10 parts of fat-soluble vitamin-containing fatty material with from 75 to 90 parts of finely divided vegetable material having a relatively high aflinity for fatty materials, and mixing the product thus obtained with from 3 to 20 parts of crude vegetable oil, the amount of fatty material incorporated into the vegetable material being controlled to yield a substantially non-oily product containing between about 5 and about 30 per cent of fatty material.

3. The process of claim 1 wherein the finely divided vegetable material used is wheat germ pressed cake flour.

4. The process of claim 1 wherein the finely divided vegetable material used is linseed oil meal.

5. The process of claim 1 wherein the finely divided vegetable material used is dried distiller's grain solubles.

6. The process of claim 1 wherein the finely divided vegetable material used is characterized by containing a natural antioxidant.

7. A process for preparing a stable, fat-soluble vitamin food product in a dry form which comprises admixing a crude vegetable oil containing dissolved therein a fat-soluble vitamin-containing material with finely divided vegetable material having a relatively high affinity for fatty material, the amount of fatty material incorporated into the vegetable material being controlled to yield a substantially non-oily product containing not more than about per cent of fatty material.

8: A process for preparing a stable fat-soluble vitamin-containing food product in a dry form which comprises admixing fat-soluble vitamincontaining material and a crude vegetable oil with finely divided vegetable material, and subsequently contacting the product obtained with a highly polar solvent substantially immiscible with fatty material in order to reduce any oiliness of the product, and then driving off the solvent by means of heat.

LORAN 0. BUXTON.

HARRY J. KONEN. 

